CN115312776B - Preparation method of high specific energy composite solid-state positive electrode - Google Patents
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
A preparation method of a high specific energy composite solid-state positive electrode belongs to the technical field of solid-state batteries, and specifically comprises the following steps: step one, dissolving polyethylene oxide, lithium salt and ethylene carbonate in an organic solvent to obtain a solution A; step two, uniformly stirring the solution A, the anode active material and the conductive agent to obtain anode slurry A; step three, uniformly dividing the anode slurry A into a plurality of groups, and respectively adding active inorganic fillers with different mass fractions into the anode slurry A to obtain anode slurry B; coating a plurality of groups of positive electrode slurry B on the surface of the positive electrode current collector in sequence to obtain a positive electrode plate, wherein the mass fraction of the active inorganic filler in the positive electrode slurry B is gradually decreased from one end close to the current collector to one end far away from the current collector; and step five, drying and tabletting the positive plate prepared in the step four to obtain the composite solid positive plate. The active inorganic filler initiates the plasticizer to undergo ring-opening polymerization, so that the ionic conductivity of the composite solid-state anode is improved, and the power density of the battery is further improved.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a preparation method of a high specific energy composite solid-state positive electrode. In particular to a method for preparing a practical high-energy and high-power density battery composite solid positive electrode by utilizing active inorganic filler LLZTO which is distributed in a gradient manner in a thick electrode to open a loop on ethylene carbonate so that a binder/electrolyte close to one side of a current collector has higher conductivity.
Background
With the rapid development of electric automobiles, portable devices and various flexible wearable devices, the demands for battery energy storage devices with lighter weight, smaller volume and higher output voltage and energy density are expanding. Commercial use of currently used embedded cathode materials, electrolytes, and graphite anode systemsLithium ion batteries are approaching the limit of their specific energy. On the one hand, high capacity active materials, such as metallic lithium negative electrodes and high nickel ternary positive electrodes, have been continually explored for higher theoretical capacities. The solid lithium battery adopts solid electrolyte, has the characteristics of incombustibility, high temperature resistance, no corrosion and no volatilization, is hopeful to reach 500 Wh/kg in battery energy density, has the development potential of solving the technical bottleneck problem of the current liquid lithium ion battery, and is an ideal chemical power supply for electric automobiles and large-scale energy storage. On the other hand, the microstructure of the positive electrode, the negative electrode and the electrolyte is optimized to improve the energy/power density of the battery, and a thick electrode hopefully achieves a high-energy density battery system design, and 500Wh kg is achieved for a Li-NMC battery -1 The minimum anode capacity of the target energy density is 30-40 mg cm -2 . However, since the thick electrode prepared by the conventional solution casting method has slow charge transport kinetics and low mechanical strength, the utilization rate of active materials is low, and the rate performance is poor. In solid-state batteries, this problem is even more pronounced because the solid electrolyte conductivity is lower than in conventional liquid electrolytes. The conductivity of the liquid electrolyte can reach 10 -2 To 10 -1 S/cm, in contrast, the solid electrolyte conductivity is 1 to 2 orders of magnitude lower, and the power and energy density of the battery are limited due to the low conductivity and the large internal resistance of the battery. In the thick electrode, active materials near the current collector are difficult to be fully utilized due to the limitation of ion transport. To address the above challenges, it is desirable to construct electrodes with different microstructures or compositions at different depths of the thick electrode, reduce the resistance during electron and ion transport directions, compensate for the reactive polarization, and thus achieve high energy and fast charge capability.
Disclosure of Invention
The invention provides a preparation method of a high specific energy and high power solid-state anode with simple operation and excellent performance by taking a battery anode as a research object. The gradient composite solid-state anode prepared by the invention has the advantages of uniform distribution of the whole charge state of ions, high utilization rate of active substances and good rate capability.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the high specific energy composite solid-state positive electrode comprises the following steps:
step one, dissolving polyethylene oxide, lithium salt and ethylene carbonate in an organic solvent to obtain a solution A;
step two, uniformly stirring the solution A, the anode active material and the conductive agent to obtain anode slurry A;
step three, uniformly dividing the anode slurry A into a plurality of groups, and respectively adding active inorganic fillers with different mass fractions into the anode slurry A to obtain anode slurry B, wherein the active inorganic fillers are LLZTO;
coating a plurality of groups of positive electrode slurry B on the surface of the positive electrode current collector in sequence to obtain a positive electrode plate, wherein the mass fraction of the active inorganic filler in the positive electrode slurry B is gradually decreased from one end close to the current collector to one end far away from the current collector;
and step five, heating the positive plate prepared in the step four at 60-150 ℃, and tabletting at 25-150 ℃ to obtain the composite solid positive plate.
Further, in the third step, in each group of positive electrode slurry B, the mass fraction of the active inorganic filler is 0% -30%.
Further, the mass ratio of the positive electrode active material, the conductive agent and the composite electrolyte is 6-9: 0.5-2: 0.5-2, wherein the composite electrolyte comprises polyethylene oxide, lithium salt, active inorganic filler and ethylene carbonate, and the proportion of the polyethylene oxide, the lithium salt, the active inorganic filler and the ethylene carbonate is 6-10: 1-4: 0-3: 1-5.
Further, in the first step, the lithium salt is lithium perchlorate LiClO 4 Lithium hexafluorophosphate LiPF 6 Lithium bisoxalato borate LiBOB, lithium difluorooxalato borate LiODFB, lithium bistrifluoromethanesulfonyl imide LiTFSI, lithium hexafluoroarsenate LiAsF 6 Lithium tetrafluoroborate LiBF 4 One of them.
In the second step, the positive electrode active material is one or more of lithium iron phosphate, lithium cobalt oxide, lithium manganate, lithium vanadium phosphate, lithium nickel cobalt aluminate and nickel cobalt manganese ternary positive electrode materials.
Further, in the second step, the conductive agent is one or more of carbon Super P, acetylene black, carbon nanotube CNT, and ketjen black.
Further, in the third step, the active inorganic filler has a diameter of 500
~10/>
。
Further, in the first step, the average molecular weight of the polyethylene oxide is 5 ten thousand to 1000 ten thousand.
Further, in the fourth step, the positive electrode slurry B is divided into at least three groups.
Further, in step four, the positive electrode current collector includes, but is not limited to, aluminum foil, aluminum mesh, aluminum foil coated with a conductive carbon layer, aluminum coated polymer film, conductive polymer film, and any other conductive film having corrosion stability for use in a battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) In the invention, the active inorganic filler LLZTO triggers the plasticizer EC to carry out ring-opening polymerization, so that the ionic conductivity of the composite solid-state positive electrode is improved, and the power density of the battery can be improved.
(2) The invention adopts the active inorganic filler LLZTO to initiate EC ring-opening polymerization, and does not adopt an additional initiator, thereby avoiding adverse effects of external impurities on the battery, reducing the occurrence of interface impedance and interface side reaction, and improving the cycling stability of the whole battery;
(3) The LLZTO adopted by the invention initiates EC ring opening to improve the strategy of the ionic conductivity of the positive electrode, and the ring opening polymerization process is carried out in the processes of removing the solvent from the positive electrode material and rolling, so that the operation flow is simple and convenient.
(4) The high specific energy composite solid positive electrode prepared by the invention has the advantages that the process of converting solid into liquid and then into solid is carried out in the ring opening process EC, so that gaps generated by volatilization of a positive electrode solvent can be filled, and the energy density of the positive electrode is improved.
(5) The gradient ring-opening strategy adopted by the invention avoids the problems of low ionic conductivity, difficult complete utilization of active substances and nonuniform charge state at one side close to a current collector in a conventional thick electrode, realizes the overall charge balance of the positive electrode, improves the stability of the positive electrode material, and prolongs the service life of the battery.
(6) The invention provides a new thought for the preparation and optimization of the high specific energy solid-state anode, and is beneficial to the industrialization of all-solid-state batteries.
Drawings
FIG. 1 is a schematic structural diagram of a composite solid-state positive electrode prepared according to the present invention;
FIG. 2 is an SEM image of the composite solid state anode prepared;
fig. 3 is a graph showing the cycle performance of the solid-state battery obtained in example 1 at a current density of 0.5C;
fig. 4 is a cycle performance chart of the solid-state battery obtained in example 2 at a current density of 0.5C.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and examples of the present invention, and it is apparent that the described examples are only some, but not all, of the examples of the present invention, and all other examples obtained by those skilled in the art without making any inventive effort are included in the scope of protection of the present invention.
Detailed description of the preferred embodiments
The preparation method of the high specific energy composite solid-state positive electrode comprises the following steps:
step one, dissolving polymer electrolyte polyethylene oxide, lithium salt and plasticizer ethylene carbonate in an organic solvent in a glove box to obtain a solution A; the dissolution conditions were: magnetically stirring at 60 deg.C for 12-24 hr.
Stirring the solution A, the anode active material and the conductive agent in a magnetic stirrer for 8-24 hours, and uniformly mixing to obtain anode slurry A;
step three, uniformly dividing the anode slurry A into a plurality of groups, and respectively adding active inorganic fillers with different mass fractions into the anode slurry A to obtain anode slurry B, wherein the active inorganic fillers are LLZTO;
coating a plurality of groups of positive electrode slurry B on the surface of the positive electrode current collector in sequence to obtain a positive electrode plate, wherein the mass fraction of the active inorganic filler in the positive electrode slurry B is gradually decreased from one end close to the current collector to one end far away from the current collector; each positive electrode slurry B is coated, and the positive electrode plate is dried; or after the coating of the anode slurry B is finished, drying the anode plates;
step five, the method 1, the positive pole piece prepared in the step four is heated and dried at 60-150 ℃, the plasticizer EC is subjected to ring opening under the initiation of the active inorganic filler LLZTO to improve the ionic conductivity of the positive pole, and meanwhile, the solvent volatilized gap is filled due to EC ring opening polymerization, so that the specific energy of the positive pole is improved; and tabletting the dried positive electrode plate in an oil press to obtain the required high specific energy composite solid positive electrode. Method 2: and (3) heating and drying the positive electrode sheet prepared in the step four in a vacuum oven at 80 ℃, taking out, pressing the composite positive electrode for 2-10 min under the pressure of 0.5-10 MPa at 100 ℃ under a hot press, opening a ring of a plasticizer under the initiation of an active inorganic filler to improve the ionic conductivity of the positive electrode, filling the volatilized gaps of a solvent due to EC ring-opening polymerization, improving the specific energy of the positive electrode, and obtaining the required high specific energy composite solid positive electrode, wherein the structural schematic diagram is shown in figure 1.
Further, in the third step, in each group of positive electrode slurry B, the mass fraction of the active inorganic filler is 5% -30%.
Further, the mass ratio of the positive electrode active material, the conductive agent and the composite electrolyte is 6-9: 0.5-2: 0.5-2, wherein the composite electrolyte comprises polyethylene oxide, lithium salt, active inorganic filler and ethylene carbonate, and the proportion of the polyethylene oxide, the lithium salt, the active inorganic filler and the ethylene carbonate is 6-10: 1-4: 0-3: 1-5.
Further, in the first step, the lithium salt is lithium perchlorate LiClO 4 Lithium hexafluorophosphate LiPF 6 Lithium bisoxalato borate LiBOB, lithium difluorooxalato borate LiODFB, lithium bistrifluoromethanesulfonyl imide LiTFSI, lithium hexafluoroarsenate LiAsF 6 Lithium tetrafluoroborate LiBF 4 One of them.
In the second step, the positive electrode active material is one or more of lithium iron phosphate, lithium cobalt oxide, lithium manganate, lithium vanadium phosphate, lithium nickel cobalt aluminate and nickel cobalt manganese ternary positive electrode materials.
Further, in the second step, the conductive agent is one or more of carbon Super P, acetylene black, carbon nanotube CNT, and ketjen black.
Further, in the third step, the active inorganic filler has a diameter of 500
~10/>
。
Further, in the first step, the average molecular weight of the polyethylene oxide is 5 ten thousand to 1000 ten thousand, and preferably, the average molecular weight of the polyethylene oxide is 10 ten thousand to 60 ten thousand.
Further, in the fourth step, the positive electrode slurry B is three groups, and the mass fraction of the active inorganic filler in the positive electrode slurry B is sequentially as follows: 30%, 20% and 10%.
Further, in step four, the positive electrode current collector includes, but is not limited to, aluminum foil, aluminum mesh, aluminum foil coated with a conductive carbon layer, aluminum coated polymer film, conductive polymer film, and any other conductive film having corrosion stability for use in a battery.
Further, in the fourth step, the positive electrode slurry B is coated on the surface of the positive electrode current collector by a method including, but not limited to, a doctor blade coating method, an extrusion coating method, a transfer coating method, a screen printing method, or an inkjet printing method.
Further, in the first step, the organic solvent includes one or more of acetonitrile, N dimethylformamide, N dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, ethanol, propanol, isopropanol, butanol, toluene, xylene, methyl ethyl ketone, dimethyl sulfoxide, tetrahydrofuran, dioxane, ethyl acetate, methyl formate, chloroform, dimethyl carbonate, diethyl carbonate, acetic acid, acrylic acid, chloroacetic acid, ethylene glycol, glycerin, and water.
The composite solid-state positive electrode provided by the invention has the advantages that the positive electrode active material provides the charge and discharge capacity of the battery, and the conductive carbon black plays a role in electronic conduction. In the composite solid electrolyte, polyethylene oxide PEO is used as a binder, and simultaneously plays a role in conducting lithium ions together with lithium salt, and the plasticizer can improve the ion conductivity of the electrolyte. The gradient change of the active inorganic filler in the electrolyte plays at least 2 roles, the active inorganic filler can be added to improve the lithium ion conduction rate of the electrolyte, meanwhile, under the heating condition, the active inorganic filler is used as an initiator to induce the plasticizer to open loop, and the ionic conductivity of the composite solid anode is further improved by the open loop polymerization of the plasticizer. In the composite solid-state positive electrode, the content of the active inorganic filler is increased in a gradient manner from one side close to the electrolyte to one side close to the current collector, the proportion of ring-opening polymerization of the plasticizer EC is increased sequentially, and the ionic conductivity is increased gradually, so that the problem of non-uniform state of charge in a traditional thick electrode, especially in a thick electrode of a solid-state battery system, is solved, the ionic conductivity of a battery positive electrode material and the utilization rate of active substances are improved, and further the power and the energy density of the battery are improved.
Example 1
The embodiment provides a simple preparation method of a high specific energy composite solid-state positive electrode, which comprises the following specific preparation steps:
(1) 2 g polyethylene oxide PEO and 0.80 g bis (trifluoromethanesulfonyl imide) Lithium (LiTFSI) are weighed in a glove box, 1.5 g Ethylene Carbonate (EC) is added into a 250 mL blue mouth bottle, then 30 g acetonitrile solvent is added, after the cap is covered and sealed, the glove box is taken out, and then the glove box is placed on a magnetic stirrer for heating and stirring, wherein the heating temperature is set to 60 ℃ and the stirring time is 24h, so that a composite electrolyte solution A is obtained.
(2) The preparation method comprises the steps of weighing 6 g positive electrode active material lithium iron phosphate (LFP) positive electrode active material, adding 0.75 g conductive carbon nano tube and 6 g composite electrolyte solution A into a weighing bottle, then placing the weighing bottle on a magnetic stirrer for heating and stirring, wherein the heating temperature is set to 60 ℃, and the stirring time is set to 12 h, so as to obtain positive electrode slurry A.
(3) The positive electrode slurry A is evenly divided into three groups, 0.6 g, 0.4 g and 0.2 g inorganic filler LLZTO are respectively added into the three groups, and then the three groups are placed on a magnetic stirrer for heating and stirring, the heating temperature is set to 60 ℃, and the stirring time is set to 12 h, so that the positive electrode slurries I, II and III are obtained.
(4) And coating the anode slurry I on an anode current collector, and placing the pole piece in a vacuum oven for vacuum drying at 100 ℃ for 12 h after coating, so as to obtain an anode coating I. And coating the positive electrode slurry II on the positive electrode coating I, and then placing the pole piece in a vacuum oven for vacuum drying at 100 ℃ for 12 h to obtain the positive electrode coating II. Sequentially, the positive electrode slurry III is coated on the positive electrode coating II, and then the pole piece is placed in a vacuum oven for vacuum drying at 100 ℃ for 12 h. EC in the positive electrode slurry initiates ring-opening polymerization by LLZTO at high temperature.
(5) And (3) taking the composite anode with the solvent removed in the step (4) out of the oven, and then placing the composite anode in a cold isostatic pressing (room temperature, 2 MPa) environment for standing for 5 min to obtain the high specific energy composite solid anode.
Example 2
The embodiment provides a simple preparation method of the high specific energy gradient composite solid-state positive electrode. The preparation method comprises the following specific steps:
(1) 2 g polyethylene oxide PEO and 0.80 g bis (trifluoromethanesulfonyl imide) Lithium (LiTFSI) are weighed in a glove box, 1.5 g Ethylene Carbonate (EC) is added into a 250 mL blue mouth bottle, then 30 g acetonitrile solvent is added, after the cap is covered and sealed, the glove box is taken out, and then the glove box is placed on a magnetic stirrer for heating and stirring, wherein the heating temperature is set to 60 ℃ and the stirring time is 24h, so that a composite electrolyte solution A is obtained.
(2) The preparation method comprises the steps of weighing 6 g positive electrode active material lithium iron phosphate (LFP) positive electrode active material, adding 0.75 g conductive carbon nano tube and 6 g composite electrolyte solution A into a weighing bottle, then placing the weighing bottle on a magnetic stirrer for heating and stirring, wherein the heating temperature is set to 60 ℃, and the stirring time is set to 12 h, so as to obtain positive electrode slurry A.
(3) The positive electrode slurry A is evenly divided into three groups, 0.6 g, 0.4 g and 0.2 g inorganic filler LLZTO are respectively added into the three groups, and then the three groups are placed on a magnetic stirrer for heating and stirring, the heating temperature is set to 60 ℃, and the stirring time is set to 12 h, so that the positive electrode slurries I, II and III are obtained.
(4) And coating the positive electrode slurry I on the positive electrode current collector to obtain a positive electrode coating I, and coating the positive electrode slurry II on the positive electrode coating I to obtain a positive electrode coating II. Sequentially, the positive electrode slurry III is coated on the positive electrode coating II, and after the coating process is finished, the pole piece is placed in a vacuum oven for vacuum drying at 80 ℃ for 12 h.
(5) And (3) taking the composite anode with the solvent removed in the step (4) out of the oven, placing the composite anode in a hot isostatic pressing (100 ℃ and 2 MPa) environment, standing for 20min, and initiating the EC in the solidified composite solid anode to polymerize, so as to obtain the high specific energy composite solid anode.
Fig. 2 is an SEM image of the prepared composite solid positive electrode, and the composite solid positive electrode binder prepared by the invention is tightly connected with active substances, and has good ionic conductivity.
Fig. 3 is a graph showing the cycle performance of the solid-state battery obtained in example 1, wherein the initial cycle discharge specific capacity of the battery can reach 155 milliamp hours per gram at a temperature of 25 ℃ and a current density of 0.5C, and the capacity retention rate after the battery is cycled for 50 cycles is 95%.
Fig. 4 is a graph showing the cycle performance of the solid-state battery obtained in example 2, wherein the initial cycle discharge specific capacity of the battery can reach 155 milliamp hours per gram at a temperature of 25 ℃ and a current density of 0.5C, and the capacity retention rate after the battery is cycled for 50 cycles is 90%.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (8)
1. The preparation method of the high specific energy composite solid-state positive electrode is characterized by comprising the following steps of:
step one, dissolving polyethylene oxide, lithium salt and ethylene carbonate in an organic solvent to obtain a solution;
step two, uniformly stirring the solution, the anode active material and the conductive agent to obtain anode slurry A;
step three, uniformly dividing the anode slurry A into a plurality of groups, and respectively adding active inorganic fillers with different mass fractions into the anode slurry A to obtain anode slurry B, wherein the active inorganic fillers are LLZTO; the mass fraction of the active inorganic filler is 0% -30%;
wherein, the mass ratio of the polyethylene oxide, the lithium salt, the active inorganic filler and the ethylene carbonate is 6-10: 1 to 4:0 to 3:1 to 5;
coating a plurality of groups of positive electrode slurry B on the surface of the positive electrode current collector in sequence to obtain a positive electrode plate, wherein the mass fraction of the active inorganic filler in the positive electrode slurry B is gradually decreased from one end close to the current collector to one end far away from the current collector; the positive electrode slurry B is divided into at least three groups;
and step five, heating the positive plate prepared in the step four at 60-150 ℃, and tabletting at 25-150 ℃ to obtain the composite solid positive plate.
2. The method for preparing the high specific energy composite solid-state positive electrode according to claim 1, which is characterized in that: the mass ratio of the positive electrode active material to the conductive agent to the composite electrolyte is 6-9: 0.5 to 2: 0.5-2, the composite electrolyte comprises polyethylene oxide, lithium salt, active inorganic filler and ethylene carbonate.
3. The method for preparing the high specific energy composite solid-state positive electrode according to claim 1, which is characterized in that: in the first step, the lithium salt is lithium perchlorate LiClO 4 Lithium hexafluorophosphate LiPF 6 Lithium bisoxalato borate LiBOB, lithium difluorooxalato borate LiODFB, lithium bistrifluoromethanesulfonyl imide LiTFSI, lithium hexafluoroarsenate LiAsF 6 Lithium tetrafluoroborate LiBF 4 One of them.
4. The method for preparing the high specific energy composite solid-state positive electrode according to claim 1, which is characterized in that: in the second step, the positive electrode active material is one or more of lithium iron phosphate, lithium cobalt oxide, lithium manganate, lithium vanadium phosphate, lithium nickel cobalt aluminate and nickel cobalt manganese ternary positive electrode materials.
5. The method for preparing the high specific energy composite solid-state positive electrode according to claim 1, which is characterized in that: in the second step, the conductive agent is one or more of carbon SuperP, acetylene black, carbon nanotube CNT and ketjen black.
6. The method for preparing the high specific energy composite solid-state positive electrode according to claim 1, which is characterized in that: in the third step, the diameter of the active inorganic filler is 500 nm-10 mu m.
7. The method for preparing the high specific energy composite solid-state positive electrode according to claim 1, which is characterized in that: in the first step, the average molecular weight of the polyethylene oxide is 5 ten thousand to 1000 ten thousand.
8. The method for preparing the high specific energy composite solid-state positive electrode according to claim 1, which is characterized in that: in the fourth step, the positive current collector comprises aluminum foil, aluminum mesh or aluminum foil coated with a conductive carbon layer.
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